Data associated with the publication: Tailored polyMOFs for ion transport in lithium-based battery electrolyte

Owing to their low flammability, solid-state and quasi-solid-state electrolytes are safer alternatives to liquid organic electrolytes for energy storage applications. Metal-organic frameworks, with facile functional tunability, long-range order, and rich host-guest interactions, have been implemented as electrolyte materials in a wide range of energy storage applications. In this work, we investigate a class of MOFs called polyMOFs as quasi-solid-state electrolyte materials. Unlike MOF-polymer composites, which are physical mixtures of MOF particles and polymers, polyMOFs are composed of polymeric linkers and metal ion nodes that self-assembled into crystalline and porous framework materials. PolyMOFs thus marry the ionic transport properties of liquid electrolyte and polymers with the synthetic versatility and host-guest interactions of MOFs. We demonstrate that the functionality of the polymer backbone of the polyMOF linker can improve room-temperature ion transport in the material. The poly(ethylene glycol) (PEG) based polyMOFs exhibit greater ionic conductivity, lithium transference number, and lower activation energy than its polyethylene (PE) analog. Supported by solid-state 7Li nuclear magnetic resonance spectroscopy, we propose these improvements are due to stronger coordination of Li+ to oxide sites in PEG, allowing for dissociation of Li and its associated anion. DFT studies further reveal that the confined solvent molecule mediates Li⁺ transport in PEG-functionalized UiO-66 framework via a metastable adsorption and hopping mechanism. This work lies at the interface of inorganic and polymer electrolytes, unveiling fundamental insights into the design of next-generation ion conductive materials for energy technologies.